Triphenylmethane dye and process of making same.



and OSWALD SCI-IARFENBERG, of

trimaran srarns WILHELM HERZBERG AND OS\VALD SOHA trlinsee ;"orfeiaatin,

GERMANY, ASSIGNORS TO AUIEN GESELLS'CHAFT itl ilt ANILIN FABRIKAIION, OFBERLIN, GERMANY.

TRIPHENYLQIIETHANE DYE AND PROCEiSS OF MAMNQ SAEJlE:

Specification of Letters Patent.

Patented Nov. is, 1906.

Appli tio filed February 3,1906 Serial No. 299.284. (Specimensd To allwhom, it Duty concern:

Be it known that we, WILHELM HERZBERG Berlin, in the Kingdom of Prussia,German Empire, have invented new and useful Improvements in new Dyestuffof the Triphenylmethane Se ries and Process of Making Same; and we dohereby declare that the following is a full, clear, and exactdescription thereof, which will enable others skilled in the art towhich it appertains to make and use the same;

Our present invention relates to the manufacture of a new dyestuii cfthe triphenylmethane series, as we have found that by condensing orthoamidophenyl -et-her-para sulfonic acid withtetraethyldiamidobenzhydrole, introducing a second sulfonic group intothe con densation product and then substituting a hydrogen atom for theamido group, there is obtained a new leuco compound the correspondingoxidation product of which is a new and very valuable acid dyestuffdyeing wool fro'n'r an acid-bath clear greenish-blue shades of a goodfastness to alkalies. The new col oring-matter possesses also leveldyeing.

In order to illustrate our invention, we give the following example, theparts of which being by weight: Sixty-five parts oftet-raethyldiamidobenzhydrole and fifty-four and one-half parts ofortho-amidophenylether-parasulfo'nic acid are dissolved to- 4 gether infive hundred parts of water with the addition of thirty-two parts of'concentrated sulfuric acid, (66 Baugn.) This mixture is heated to 95-100centigradc during twenty-four hours. On cooling the condensation productseparates outas sulfate in the shape of small brilliant leaves and isisolated in the usual manner. One hundred parts of the sulfate thusobtained are poured into two hundred parts of concentrated sulfuric acidof onc hundred-per-cent. strength monohydrate) and the mass heated to6070, the end of the reaction being shown by the fact that a sample ofthemass'dissolves totally in a solution of sodium ,carbonat'e. It; orderto isolate the disulfonic acid formed, the mass is diluted with threelumdred to fear hundred parts of ice and water and then allowed to' jstand'for some time, whereaftcr the largest part of the reaction productseparates out also as sulfate. It is isolated by filtering and drying.

Eliminating, the amido group is carried out as follows: One prepares anaqueous solution ter about three parts of cuprous oxid are added whilestirring well. The reaction begins at once, nitrogen gas being evolved.As soon as the diazo compound has totally decomposed the alcohol isdistilled off.

In order to form the dyestuif by oxidation of the leuco-sulfonic acid,one may use the sofrom the copper. The oxidation is then perperoxid(P1303) and sulfuric acid. After. oxivdation the solution is separatedfrom the lead sulfate formed during the reaction by filtering. Thedyestuff is then precipitated by means of sodium sulfate and isolated byfiltering and drying. It is thus obtained in the shape of a mass havinga lusterlike copper and easily dissolving in water and alcohol to agreen-blue colored solution. The greenblue aqueous solution of the dyeis changed to green by the addition of some mineral acid. On theaddition of an excess of mineral acid it assumes a yellow coloration.Furthermore, when soda-lye is added to an aqueous solution in the coldor at ordinary temperature no change occurs, whereas on boiling such asolution a violet coloration is produced, the dyestuif being decomposed.Y in concentrated sulfuric acid the dycstufl dissolves with a weaklyyellow coloration. Some drops of water added thereto produce an intenseyellow color, whereas on adding more water the mass assumes ayellow-green coloration.

It is obvious to those skilled in the art that above example nor to thedetails given thereof the diazo compound of the above disullution freedfrom alcohol as above and filtered formed in the usual manner by meansof lead our present invention is not limited to the in. So, for;instance, instead. of first sulfonating the above condensation productand then eliminating the amido group these operations may also beperformed in the opposite si1c ssioii. i urthermore, the isolation ofthe (liSLllfUlil; acid may be carried out in any other suitableinanner-as, for instance, by preparing the calcium salts from the reacition massthus being produced the soluble calcium salt of the disulfonicacid which is separated by filtration. from the insoluble calciumsulfate.

As to the oxidation of the lcuco-disulfonic a id, for the lead peroxidin conjunction with sulfuric acid employed in the above example theremay be substituted another suitable oxidizing *nixture or compound-es,for instance, pyrolusite (MnO- in conjunction with sulfuric. acid or thelike.

Instead of the sulfuric acid used above for l the condensation ofortho-aminophenyletherpara-sulftmic acid withtetraethyl-diamidobenzhydrol another acid-condensing agent, such ashydrochloric acid or the like, may be employed.

Hating now described our invention and the manner in which the same hasto be performed, what we claim i.s

1. The herein-described process of making a new dyestufl' ofthetriphenylmethane series which process consists in condensingorthoaminoplienylether-para-sulfonic acid with tetraethyldiai'nidobenzhydrol, converting the condensation product into adisulfonic acid, elin'iinating the NH group and substi-, tuting therefora hydrogen atom and finally oxidizing the leuco compound thus obtainedto the dyostu'fi'. 2. The hereinbefore-' lcscribed process of making anew dyestufl' of the triphenylmethane series which process consists incon- (lensing ortho anunophenylether para sulfonic acid withtetraethyl-diamidobenzhy-l drol by means of sulfuric acid, sulfonatingthe condensation product with concentrated sulfuric acid, eliminatingfrom the disulfonic acid formed the group by diazotizing it and treatingthe diazo compound with alco hol in the presence of copper and finallyoxidizing the leuco compound thus obtained to the dyestuil' by means ofmanganese peroxid and sulfuric acid.

3. As a new article of manufacture the liereinbefore-described newdyestufl' of the triphenyhnethane series, being in the sha e of thesodium salt a mass having a luster li (e copper, easily dissolving inwater and alcohol to a green-blue solution, the aqueous solution ofwhich dyestufl is changed togreen by the addition of some mineral acid,whereas an excess of mineral acid produces a yellow coloration, and theaqueous solution of which dyestuff is not changed in its coloration bythe addition of soda-lye in the cold or fltOI'dlllfLI'y temperature,whereas such an aqueous solution on boiling with soda-lye assumes aviolet coloration, the dyestuif being decomposed, and this dyestuffdissolving in concentrated sulfuric acid to a weakly yellow solution,which solution on addition of some drops of Water assumes an intenseyellow color, Whereas on adding more water a yellow-green coloration isproduced, and which dyestuff produees on wool, when dyed from anacid-bath, clear greenish-blue tints of a good fastness to alkalies.

In witness whereof we have hereunto signed our names, this 20th day ofJanuary, 1906, in the presence of two subscribing Witnesses.

WILHELM HERZBERG. 'OSWALD SCHARFENBERG.

Witnesses:

WOLDEMAR HAUPT, HENRY HAs PER.

